Explosive



. and the nitro compounds proper.

UNIT EDMUND VON HERZ, OF GHARLOTTENBURG, GERMANY.

Patented J an. 3, 1922.

EXPLOSIVE.

40 93 Specification of Letters Patent. I

No Drawing.

To all whom it may concern:

Be it known that EDMUND VON HERZ, a citizen of Germany, residing at 29Sybelstrasse, Charlottenburg, Germany, formerly of 48Schoubergerstrasse, Vienna, Austria, has invented certain new and usefulImprovements Relating to Explosives, (for which I have filed anapplicatlon in Austria, Jan. 25, 1919,) of which the following is aspecification.

The well known nitro explosives used in practice belong both as regardstheir chemical constitution and also their properties and effects ingeneral to two different groups, viz. the ethereal salts of nitric acidTypical representatives of the first class are nitro glycerine andguncotton, of the second the aromatic nitro compounds such astrinitrotoluene, picric acid and tetranitromethylaniline. The mostprominent features of the ethereal salts of nitric acid are on thefavourable side the high amount of energy they contain and on theunfavourable side their easy liability to decomposition and theirextraordinarily great sensitiveness towards mechanical influences. Incontradistinction hereto is the behaviour of the aromatic nitrocompounds. Their advantages are in articular their extraordinarychemical staliility and their marked non-sensitiveness towardsshock,'but their disadvantage is their comparatively low energy.

These oppositely contracted properties explain the various attemptswhich have been made to rovide an explosive, which shall combine 1nitself only the advantages of both classes of explosive, that is to saya compound, which, in addition to the stability and non-sensitiveness ofthe aromatic nitro compounds exhibits the degree of energy of theethereal salts of nitric acid. As a result of these attempts hithertoobtained, certain tetranitrated benzene derivatives with'the onlyrecently prepared tetranitraniline are the chief. These compounds aremost certainly an advance in-this direction, but they have not fulfilledthe expectations demanded of them, because, as it was subse uentlyfound, the increase in ener con erred by the fourth nitro group was 0tained at the expense of a serious decrease in their stability. Owing toa decided liability of the fourth nitro group, which is situated in themeta position, these highly Application filed October 25, 1920. SerialNo. 419,417.

nitrated substances areso liable to decom- .in itself in an absolutelyideal manner the favourable properties of the ethereal salts of nitricacid and the aromatic nitro compounds.

This new explosive substance is neither an ethereal salt of nitric acidnor a pure n1tro compound, but is a nitramine with a peculiar ringformation. As chemical investlgatlon has shown, it is derived likehexamethylenetetramine from the hypotheticalcyclotrimethylenetriamine cHN/ NH mck on,

and possesses the following structural formula:

C NOz-N \N-NOa Hack/CH: N N0:

This cyclotrimethylenetrinitramine is formed from all the accessiblederivatives of cyclotrimethylenetriamine by the action of concentratednitric acid. For its product1on on a large scale, however, onlycyclotrimethylenetrimethyltriamine, that is the condensation productobtained from formaldehyde with methylamine could be entertained as araw material in addition to the already known hexamethylenetetramine, asthe other derivatives are diflicultly accessible and therefore noteconomical.

The following method of preparation has been found to answer well breason or itsgood yield and the remarka le'uniformity of the product: I

Into 500 grms. of nitric acid of a specific gravity of 1.52 freed ascompletely as possible from nitrous gases are introduced, at first inquite smallportions, and gradually, 70 grms. of well 'dried crudehexamethylenetetramine with continuous stirring. The temperature is keptbetween and C. durlng the nitration. After the addition of thehexamethylenetetramine is complete the mixture is allowed to stand for afew minutes at the said temperature and then the mixture is slowlyheatedto 55 C. By continuous stirring and cooling if necessary thetemperature is kept between 50 and 55 for a period of about 5 minutesafter which the mass is again cooled down to the original temperature.After 15 minutes standing it is diluted whilst being again cooled by thequite gradual addition of from 3 to 4 times its volume of water andafter some time the separated nitro compound is separatedfrom theliquid. After being washed several times with cold water, hot dilutesoda soluity.

tion and again with water it is finally dried at any desiredtemperature. If necessary the product may also be recrystallized fromacetone.

T h e cyclotrimethylenetrinitramine o b tained in this way is abrilliantly white, odourless and tasteless rather coarsely crystallinepowder of a neutral reaction. It melts at 200 C. and only detonates athigher temperatures. It is quite insoluble in water, difiicultly solublein hot alcohol more easily so in acetone glacial acetic acid andvconcentrated nitric acid from which substances it can also berecrystallized.

The cyclotrimethylenetrinitramine is not attacked by either boilingwater nor by hot dilute acids and exhibits when subjected to the usualhot storage tests even at unusuall high temperatures quite a remarkabestabi It is extraordmaril non-sensitive'towards shock, blows and rictionand in this respect is about equal to the aromatic trinitro compounds.When ignited it burns slowly without exploding with a bright reddishflame and a fizzing noise like tetranitraniline and leaves no residue.

The most su rising feature of this compound however 1s it extraordinaryexplosive and shattering power. In this respect thecyclotrimethylenetrinitramine exceeds all the explosive substanceshitherto known, both the enormously energetic nitroglycerine and alsothe rapidly detonating tetranitraniline. This propert it owes, inaddition to a composition whic permits of fairly complete internalcombustion, to its high endothermic character principally. Whereas theformation of the most of the nitro explosivea takes place withfrequently a considerable loss of ener y, the welding together of thecyclotrimet ylenetrinitramine from the elements requires theastonishingly high amount of 81.4 calories per molecule. This latentfixed energy is again manifested on explosive decomposition andincreases the amount of energy of this explosive to an unusually highamount. Hand in hand with this increase of energy there appears to bealso the velocity of detonation which is greater than that of any otherknown explosive substance. Since there is added as a third factor anextremely large volume of gas due to the large amount of nitrogen andhydrogen contained, this new explosive seems to be of quite enormouseffect, which is also clearly shown actually by the surprising resultsof the lead block and penetration tests.

Another requirement, which is demanded of a good explosive, that of ahigh density, is possessed by cyclotrimethylenetrinitramine in quite aremarkable degree. The absolute specific gravity is 1.82 and this is amaximum not possessed by any nitro coinpound hitherto. This fact enablesvery high loading densities to be obtained which is of great importancefor many purposes, e. g., bursting charges for projectiles, detonatorsand percussion caps.

The following table will show the comparison of all these constants ofexplosive science with those of other explosives.

Heat of explo- Speed Density Vol. 01 sionper otdeto- Abs at a gasperkilonatlon pres- Kmds of explosive. kilogram at max. spec sure framcalorie density 01350 ltre. (water (in per 1 kg.

gasesec.) c. m I

ous).

Trinitrotoluene 885 680 6, 770 1. 62 1. 40 Picric & (!1d 877 778 7,110 1. 74 1. 42 Tetramtromethylaniline. 932 868 7, 850 1. 728 1. 50Tetranitroanihne. 817 1, 073 7, 930 1. 76 Nitroglycerlne 712 1, 491 8,080 1. 6 Cyclotrrmethylenetrinltramme 905 1,597 8,500 1.82 1.00

A point of importance which is not to be underestimated is also thebehaviour of cyclotrimethylenetrinitramine in a sanitary di-" rection.In contradistinction to most of the other nitro compounds it isabsolutely nonpoisonous, has no tinctorial properites, is completelyodourless and tasteless and does not cause either in the form of dust orsolution any irritant affections of the respiratory organs and the skin.Injuries to the work people by the usual discolourations of the skin,injurious action on the sense of taste, eruptions, headaches and easychronic poisoning which are caused in the preparation and handlin of thenitro compounds are therefore precluded and the complicated hygienicprecautions hitherto necessary become partially superfluous.

From these remarks it will therefore be clear, that incyclotrimethylenetrinitramine wehave a perfectly new, hitherto unknorgnexplosive, which combines in itself in an ideal way the advantages bothof the ethereal salts of nitric acid and also those of the aromaticnitro compounds, combined with remarkable stability andnon-sensitiveness of the large number of excellent properties which itpossesses, all branches of civil and military explosive science. Inaddition to its use for bursting charges for projectiles, *mines, andthe like, and as a blasting agent for all mining and mineralogicalpurposes it is particularly suitable for the production ofextraordinarily rapidly acting detonating fuses and in conjunction withinitial means of ignition for the filling of: percussion caps,detonators and fuses for projectiles. According to the use for which itis required and the effect aimed at the cyclotrimethylenetrinitraminemay be .used alone, or in conjunction with or mixed with other ex- Iplosives or components of explosives.

What I claim and desire to-secure by Letters Patent of the United Statesis 0 1. An explosive device consisting of a hollow body, containing anexplosive comprising cyclotrimethylenetrinitramine.

2. A detonator cap comprisingcyclotrimethylenetrinitramine. 'v

EDMUND-yon Witnesses: Y

""1 DR. Comm) Tenenris,-' a WARNER GRoM. .o

